US3166522A

US3166522A - Organoboron polymers

Info

Publication number: US3166522A
Application number: US206191A
Authority: US
Inventors: Kitasaki Kiyoshi; George W Willcockson
Original assignee: United States Borax and Chemical Corp
Current assignee: US Borax Inc
Priority date: 1962-06-29
Filing date: 1962-06-29
Publication date: 1965-01-19
Anticipated expiration: 1982-01-19
Also published as: GB1006336A

Description

description proceeds.

United States Patent .0 M

3,166,522 ORGANOBORON POLYMERS Kiyoshi Kitasahi, Garden Grove, and George W. Willcockson, Anaheim, Calif., assignors to United States Borax & Chemical Corporation, Los Angeles, Calif., a corporation of Nevada V N Drawing, Filed June 29, 1962, Ser. No. 206,191

' v13 Claims. c1. 2 0-4 The present invention relates as indicated to a new class of organoboron polymers and has further reference to a method for'preparing these polymers.

It is, therefore, the principal object of the present invention to provide a new class of thermally stable organoboron polymers.

It is a further object of this invention to provide an efiicient and economically desirable method for preparing these therrnally'stable organoboron polymers.

Other objects of .the present invention will appearas the To the accomplishment of the foregoing and related ends, said invention then comprises the features hereintaining a total of from 2 to carbon atoms, cycloalkylene radicals, the cyclic portion of which is of from 4 to .6 carbon atoms and containing a total of irom 4 to 2-0 carbon atoms, 1,3-phenylene and 1,4-phenylene.

The 'organoboron polymers of the. present invention are thermally stable at temperatures up to 500 C.,' and they havenu-rnerous industrial applicationsas protective coatings for heat sensitive materials which are to be subjected to high temperature environments. Additionally, the present polymers have excellent adhesive properties, and they have utility in the bonding of such materials as glass, wood and metal, and in the preparation of Fiberglas laminates. The preparation of the present organoboron polymers can best be illustrated by the following equation:

1h ,7 Where R is hydrogen, an alkyl -radic'al of frorri 1: jt(:)8 an bon atomsgphenyl or tolyl, and Xiseither'an alkylene 3,166,522 Patented J n; 19, 1965 Thepre'ferred .method for performing-the foregoing polymerizationreaction is a' direct single-step process, A 5.,5' bis(2-'oxy-1,3,2-benzodioxa=borole) "and an applicable di-hydric alcohol are admixed either in the presence or absence of a solvent which is inert to the reactants. The

' reaction mixtureis then heated under reflux and the alcoradical of from 2"to 20 canbonatoms in length'and' con-f taining a 'totalyof frorn 2to 20 carbon atoms, acycloalkylene radical, the cyclic portion of which is offrom 4 to 6] carbon atoms and containing a total of from 4 to 20 carbon atoms," or a 1,3-phenylene'orf1,4-phenylene f Y "5,5'- bis(2-cresyloxy 1,3,2=4benzodioxaborole) radicalp 1 1101 or water reaction by-product is continuously removed from the reaction mass by distillation. After substantially all'of the reaction lay-product has been removed, the desired organoboron polymer is recovered by standard methods. H a As regards the reactants applicable to the present invention, the first of these are the 5,5'-.bis(2-oxy-l,3,-2- benzodioxa borole) compounds having the formula where R is either hydrogen, an alkyl radical of from 1 'to 8 carbon atoms, phenyl or tolylp The 5,5'-bis(2-organooxy-l,3,24benzodioxaboroles) are prepared by the reaction of an orthoborate esterwith bis(3,4-dihydroxyphenyl) and the;5,5'-bis(2-hydroxy-l,3,2-benzodioxaborole) is obtained by the hydrolysis of any of the 5,5'-1bis(2 organooxy-l,'3,2+benzodioxaborole) compounds.

The following examples are-given to illustrate the preparation of the 5,5 'b-is(2-oxy-l,3,2-benzodioxaboroles) borole). Chemical analysis of theproduct yielded the following data: l 1

Calculated for 013132 13205; Found in product: C=60.63%', H=5.75%, B=6.07%. Q a r Water, 0.72 gram (0.04 mole), was added to a solution of 6.52 grams (0.02 mole) of 5,'5-bis(2-ethoxy-1,3,2 benzodioxaborole) in ml. of veratrole, The mixture was diluted with benzene, cooled and filtered to' yield 5.01

grams (92.7% yield) of .5,5'- bis(2-hydroxy-l,3,2-benzodioxaborole). Chemical analysisof, the product yielded "The following list is illustrative o-fthe 5, 5 -bis(2-oxyl,3,2 laenzod-ioxaboroles) which can be prepared in this rnanner, and which are applicable to the present invention:

5 ,S'abis (2-isopropoxyd,3,2-ibenzodioxa borole)" 5,5"-bis(Z-n-hexyloxy-l,3,24benzodioxaborole)- 5,5'4bis(Z-sec-butoxy-l,3,2-1benzodioxaborole) 5,5 '-4b is(2-noctyloxy-1,3,-2=benzodioxaborole) 5,5'-bi-s(2phenoxy-1,3,2 benzodioxalbo role) where X is either an alkylene radical of from 2 to 20 carbon atoms in length and containing a total of from 2 to 20 carbon atoms, a cycloalkylene radical, the cyclic portion of which is of from 4 to 6 carbon atoms and which contains a total of from 4 to 20 carbon atoms, or a 1,3-phenylene or a 1,4-phenylene radical. Thus, these compounds are either alkylene diols, cycloalkylene diols, 1,3-phenylene diol, or 1,4-phenylene diol.

It will be noted here that the alkylene diols applicable to the present invention include both branched and straight-chain alkylene groups, and also include diols having the. two hydroxyl groups bonded to alkylene radicals Where the chain also includes olefinic groups, acetylenic groups, cycloalkyl groups, or phenyl groups. The cycloalkylene diols are those diols having the two hydroxyl groups bonded directly to the cyclic portion of the cycloalkylene radical.

The following list is illustrative of the dihydric alcohols applicable to the present invention:

Resorcinol Hydroquinone 1,Z-diphenyl-1,2-ethanediol 1,2-ethanediol 2,3-dimethyl-2,3-butanediol 1,3-propanediol 2,4-pentanediol 2,3,3 ,4-tetramethyl-2,4-pentanediol 2,3-dimethyl-1,3-propanediol 1,4-butanediol 2-methyl-2,5-pentanediol 1,4-hexanediol 2,5-dimethyl-2,5-hexanediol 1,7-heptanediol 1', l O-decanediol 1,14-tetradecanediol 1,12-octadecanediol 1,18-octadecanediol 1-butenediol-3,4

2-butenediol-1,4

2-butynediol-1,4 2,5-dimethyl-3-hexynediol-2,5 1,4-cyclohexanedicarbinol 1 ,2-cyclobutanedicarbinol 1,3-benzenedicarbinol 2,2,4,4-tetramethyl-1,3-cyclobutanediol 2,3-dimethyl-1,2-cyclopentanediol 1,3-cyclobutanediol 1,3-cyclopentanediol 1,3-cyclohexanediol 1,4-cyclohexanediol 2,2,5,5-tetramethyl-1,3-cyclohexanediol 1,4-dibenzyl-1,4-cyclohexanediol 2,5 ,5 -trimethyl- 1 ,4 cyclohexanediol The solvents applicable to the present invention must be inert to the reactants and to the desired products. The common aromatic hydrocarbon solvents, ethers, 'alkoxy and chloro-substituted aromatic hydrocarbons, and organo-substituted acetarnides are all-suitable for this purpose. The following list is illustrative of these com pounds:

Benzene Toluene Xylene Monochlorobenzene Dichlorobenzene Anisole Veratrole N,N-dimethylacetamide Diethyleneglycol dimethyl ether (diglyme) Tetraethyleneglycol dimethyl ether (tetraglyme) It is to be clearly understood that the foregoing lists of compounds are only a partial enumeration of the reactants and solvents applicable to the present invention and are not intended to limit the invention.

So that the present invention can be more clearly understood, the following examples are given for illustrative purposes:

III

To ml. of tetraglyme in a 500 ml. round-bottomed flask was added 6.13 grams (0.0145 mole) of 5,5'-bis(2- phenoxy-1,3,2-benzodioxaborole) and 1.60 grams (0.0145 mole) of hydroquinone. The reaction mixture was then heated under reflux for about 4 hours, at which time 2.59 grams, 94.7% of theoretical, of phenol had been removed. The reaction mass was cooled and concentrated by removing a portion of the tetraglyme by distillation at reduced pressure. The suspended solids were separated by filtration, washed with benzene and dried at about 250 C. for about 4 hours, and 4.6l grams of a white powdery polymeric material, M.P. 484493 C., was recovered. Chemical analysis of the product yielded the following data:

Calculated for C H B 'O C=62.86%, H=2.93%, B=6.29%. Found in product: C=62.23%, H=2.75%, B= 6.26%.

To 150 ml. of xylene in a 500 ml. round-bottomed flask was added 8.10 grams (0.03 mole) of 5,5-bis(2-hydroxy- 1,3,2-benzodioxaborole) and 4.33 grams (0.03 mole) of 2,2,4,4-'tetramethyl 1,3 cyclobutanediol. The reaction mixture was then heated under reflux for about 6 hours at which time 1.03 grams, 95.5% of theoretical, of water had been removed. The reaction mass was cooled and concentrated by removing a portion of the xylene by distillation at reduced pressure. ,The suspended solids were separated by filtration, washed with benzene and dried at about 150 C. for about 4 hours to yield 10.30 grams of a white, powdery polymeric material. Chemical analysis of the product yielded the following data: 1

Calculated for' C H B O C=63.55%, H=5.35%, B=5.72%. Found in product: C=62.79%, H=5.40%, B=5.79%.

To 120 'ml'. of diglyme in a 500 ml. round-bottomed flask was added 8.15 grams (0.025 mole) of 5,5-bis(2- ethoxy-l,3,2-benzodioxaborole) and 2.75 grams (0.025 mole) of resorcinol. The reaction mixture was then heated under reflux for about 5 hours at which time 2.21

Calculated for C18H10B2O6: C=62.86%, H=2.93%,

B=6.29%. Found in product: C=62.19%, H=2.80%, B=6.32%.

To ml. of veratrole in a 500 ml. round-bottomed flask was added 11.46 grams (0.03 mole) of 5,5'-bis(2-nbutoxy-1,3,2-benzodioxaborole) and 3.55 grams" (0.03

7 mole) of 2-methyl-2,4-pentanediol. The reaction mixture was then heated under reflux for about 6 hours'at which time 4.19 grams, 94.2% of theoretical, of n-butanol had been removed. The reaction mass was cooled and concentrated by removing a portion of the veratrole by distillation at reduced pressure. The suspended solids were separated by filtration, washed with benzene and dried at about C. for about 4 hours to yield 9.51 grams of a white, powdery polymeric materiaL' Chemical analysis of the product yielded the following data:

Calculated for C H B O C=61.42%, H=5.14%, B=6.15%. Found in product: C=60.87%, H=5.30%, B=6.19%.

VII

To 120 ml. of toluene in a 500 ml. round-bottomed flask was added 10.62 grams (0.03 mole) of 5,5-bis(2-npropoxy-1,3,2-benzodioxaborole) and 2.58 grams (0.03 mole) of 2-butenediol-1,4. The reaction mixture was then heated under reflux for about 5 hours at which time 3.44 grams, 95.3% of theoretical, of n-propanol had been removed. The reaction mass was cooled and concentrated by removing a portion of the toluene by distillation at reduced pressure. The suspended solids were separated by filtration, washed with benzene, and dried at about 150 C. for about 4 hours to yield 8.84 grams of a white, powdery polymeric material. Chemical analysis of the product yielded the following data:

Calculated for C H B O C=59.70%, H=3.76%, B=6.72%. Found in product: C:59.13%, H=3.51%, B=6.79%.

A second satisfactorymethod for preparing the present.

organoboron polymers involves reacting an applicable diol directly with the reaction mass derived from the preparation of the 5,5'-bis(2-oxy-1,3,2 benzodioxaborole) reactant without separating the borole from the reaction mass. The following examples are illustrative of this method for preparing the present organoboron polymers.

VIII

A solution of 7.52 grams (0.04 mole) of triisopropyl borate in 10 ml. of veratrole was added to a stirred solution of 4.36 grams (0.02 mole) of bis(3,4-dihydroxyphenyl) in 100 ml. of veratrole. The solution was then heated under reflux for about 3 hours at which time 4.80 grams of isopropanol had been removed. The reaction mixture was then cooled to about 50 C. and 2.20 grams (0.02 mole) of hydroquinone was added. The resultant mixture was then heated for about another 3 hours under reflux at which time 2.30 grams of isopropanol had been removed.

Solids began to form as the reaction mass was cooled and the suspension was concentrated by removing a portion of the veratrole by distillation at reduced pressure. The solids were then recovered by filtration, and dried at about 250 C. for about 4 hours to yield-6.16 grams of a white, powdery polymeric material, M.P. 489498 C. Chemical analysis of the product yielded the following data:

Calculated for C H B O C=62.86%, H=2.93%, Found in product: C=62.18%,H=3.01%, B=6.27%.

A solution of 9.20 grams (0.04 mole) of tri-n-butyl borate in 10 ml. of veratrole was added to a stirred solution of 4.36 grams (0.02 mole) of bis(3,4-dihydroxyphenyl) in 100 ml. of veratrole. The solution was then heated under reflux for about 2 hoursat which time 6.0 grams of n-butanol had been removed. The solution was cooled and 2.20 grams (0.02 mole) of res'orcinol was added. The resultant mixture was then heated for about 3 hours under reflux at which time 2.79 grams of butanol had been removed. The reaction mass was then cooled and as the veratrole was being removed by distillation at reduced pressure solids began to precipitate. The veratrole was removed and the remaining solids were suspendedin benzene and recoveredby filtration. The solids were then dried'at about 250 C. for about 5 hours to yield 5.29 v

grams of a white, powdery polymericfmat'erial, M.P. 365-370 C. Chemical analysis of the product yielded the following data: 7 1

Calculated for G i-1 E 0 C=62.8 6%, H =2.93%, Found in product: C,=61.19%; H=2.81%,

The polymers of the present invention were subjected to thermogravimetric analysis to determine their thermal stability. The polymeric 1,3- and 1,4-phenylene derivatives were heated at a constant temperature increase of C. per hour at a pressure of about 10" mm. Hg. The recorded weight losses for these materials at 500 C. were in the range of from about 4 to about 10 percent. Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims or the equivalent of such be employed. We, therefore, particularly point out and distinctly claim as our invention: 7

1. Solid, thermally stable organoboron polymers consisting essentially of the recurring structural unit radicals the cyclic portion of which is of from 4'to 6 carbon atoms and containing a total of from 4 to 20' carbon atoms,"

1,3-phenylene and 1,4-phenylene.

2. Solid, thermally stable organoboron polymers consisting essentially of the recurring structural unit 3. Solid, thermally stable organoboron polymers consisting essentially of the recurring structural unit 4. Solid, thermally stable organoboron polymers, consisting essentially of the recurring structural unit 7 5. Solid, thermally stable organoboron polymers consisting essentially of the recurring structural unit i 6: Solid, thermally stable organoboron polymers e511 sisting essentially of the recurring structural unit The method for preparing solid, thermally stable organoboron polymers consisting essentiallyof the recur which comprises heating under reflux a mixture of an orthoborate ester of the formula B(OR) and bis(3,4-dihydroxyphenyl) in the presence of a solvent inert to said reactants, continuously removing the alcohol lay-product, allowing the resultant reaction mass to cool, adding a diol of the formula HOXOH to said reaction mass, heating said mixture under reflux, continuously removing the alcohol by-product and recovering said organoboron polymer from the resultant reaction mass, where X is selected from the group consisting of alkylene radicals of from 2 to 20 carbon atoms in length and containing a total of from 2 to 20 carbon atoms, cycloalkylene radicals the cyclic portion of which is of from 4 to 6 carbon atoms and containing a total of from 4 to 20 carbon atoms, 1,3- phenylene and 1,4-phenylene, and R is selected from the group consisting of alkyl of from 1 to 8 carbon atoms, phenyl and tolyl.

8. The method for preparing solid, thermally stable organoboron polymers consisting essentially of the recurring structural unit which comprises heating under reflux a mixture of a 5,5- bis(2-oxy-1,3,2-benzodioxaborale) or" the formula and a diol of the formula HO-X-OH in the presence of a solvent inert to said reactants, continuously removing the reaction by-product by distillation, and recovering said organoboron polymer from the resultant reaction mass, where X is selected from the group consisting of alkylene radicals of from 2 to 20 carbon atoms in length and containing a total of from 2 to 20 carbon atoms, cycloalkylene radicals the cyclic portion of which is of from 4m 6 carbon atoms and containing a total of from 4- to 20 carbon atoms, 1,3-phenylene and 1,47-phenylene, and R is selected from the group consisting of alkyl of from 1 to 8 carbon atoms, phenyl, tolyl and hydrogen.

9. The method for preparing solid, thermally stable organoboron polymers consisting essentially of the recurring structural unit which comprises heating under reflux a mixture of a 5,5- bis(2-oxy-1,3,2-benzodioxaborole) of the formula and hydroquinone in the presence of a solvent inert to said reactants, continuously removing the reaction bycas s which comprises heating under reflux a mixture of a 5,5-bis(2-oxy-l,3,2-benzodioxaborole) of the formula ROB/ and resoreinol in the presence of a solvent inert to said reactants, continuously removing the reaction lay-product by distillation, and recovering said organoboron polymer from the resultant reaction mass, where R is selected from the group consisting of alltyl of from 1 to 8 carbon atoms, phenyl, tolyl and hydrogen.

11. A method for preparing solid, thermally Stable organoboron polymers consisting essentially of the recurring structural unit which comprises heating under reflux a mixture of a 5,5-bis(2-oxy-l,3,Z-benzodioxaborole) of the formula ROB m BOR which comprises heating under reflux a'mixture of a 5,5-bis(2-oxy-1,3,2-benzodioxaborole) of the formula and 2-methyl-2,4-pentanediol in the presence of a solvent inert to said reactants, continuously removing the reaction by-product by distillation, and recovering said organoboron polymer from the resultant reaction mass, Where R is selected from the group consisting of alkyl of from 1 to 8 carbon atoms, phenyl, tolyl and hydrogen. 13. The method for preparing solid, thermally stable organoboron polymers consisting essentially of the recurring structural unit which comprises heating under reflux a mixture of a 1% 5,5-bis(2-oxy-1,3,2-benzodioxaboro1e) of the formula and 2-butenediol-1,4 in the presence of a solvent inert to said reactants, continuously removing the reaction by-product by distillation, and recovering said organoboron polymer from the resultant reaction mass, where R is selected from the group consisting of alkyl of from 1 to 8 carbon atoms, phenyl, tolyl and hydrogen.

References Cited in the file of this patent UNITED STATES PATENTS Salzberg et al Dec. 28, 1948 Lane Aug. 1, 1961 Trish et al. Dec. 19, 1961

Claims

1. SOLID, THERMALLY STABLE ORGANOBORON POLYMERS CONSISTING ESSENTIALLY OF THE RECURRING STRUCTURAL UNIT